CN103534274A

CN103534274A - Cellulose ester optical films

Info

Publication number: CN103534274A
Application number: CN201280017851.6A
Authority: CN
Inventors: C.M.布查南; M.E.唐纳尔逊; E.古斯曼-莫拉列斯; P.B.麦肯兹; 王斌
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2011-04-13
Filing date: 2012-03-29
Publication date: 2014-01-22
Also published as: EP2697262A1; TWI568748B; CN107254003A; US20120263889A1; US20120263890A1; CN103717621A; EP2697263B1; EP2697262B1; TWI532772B; TW201247712A; JP6082384B2; JP2014513178A; WO2012141902A1; US20120264930A1; WO2012141901A1; US9796791B2; WO2012141904A1; US10494447B2; TWI583729B; TW201245310A

Abstract

Regioselectively substituted cellulose esters having a plurality of aryl-acyl substituents and a plurality of alkyl-acyl substituents are disclosed along with methods for making the same. Such cellulose esters may be suitable for use in optical films, such as optical films having certain Nz values, -A optical films, and/or +C optical films. Optical films prepared employing such cellulose esters have a variety of commercial applications, such as, for example, as compensation films in liquid crystal displays and/or waveplates in creating circular polarized light used in 3-D technology.

Description

Cellulose ester optical film

Background of invention

1. invention field

Different embodiments of the present invention relates generally to cellulose ester composition, manufacture the method for cellulose ester composition and by the blooming of its production.Certain embodiments of the present invention relate to and have the two cellulose ester of alkyl-acyl substituent and aryl-acyl substituent, and blooming prepared therefrom.

2. association area explanation

Cellulose ester for example cellulose triacetate (" CTA " or " TAC "), cellulose acetate propionate (" CAP ") and cellulose acetate butyrate (" CAB ") is used in the various films in liquid-crystal display (" LCD ") industry.Their foremost application are as protection and compensate film, use together with polaroid.These films can typically be manufactured by solvent cast, are then laminated on the either side of polyvinyl alcohol orientation, iodate (" PVOH ") polarizing coating, prevent from that this PVOH layer is scratched with moisture to enter, and also improve structural rigidity simultaneously.When the compensate film (also referred to as wave plate), they can and polaroid stacked body laminated or be otherwise included between polaroid and liquid crystal layer.This wave plate can be for improvement of the contrast gradient of LCD, wide visual angle and colour cast performance.Although made significant headway in LCD technique, still need to improve.

Summary of the invention

A kind of embodiment of the present invention relates to the cellulose ester that a kind of regioselectivity replaces, and it comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent, hydroxyl the substitution value (" DS of the cellulose ester that wherein this regioselectivity replaces _oH") be at least 0.30, the regioselectivity of the cellulose ester that wherein this regioselectivity replaces is such, that is, and at aryl-acyl substituted degree (" C2DS of C2 and C3 _aryl" and " C3DS _aryl") aryl-acyl substituted degree (" C6DS of deducting at C6 of sum _aryl") be greater than 0.20.

Another embodiment of the present invention relates to a kind of single layer optical film; the cellulose ester that its inclusion region selectivity replaces; the cellulose ester that wherein this regioselectivity replaces comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent, hydroxyl the substitution value (" DS of the cellulose ester that wherein this regioselectivity replaces _oH") be at least 0.30, wherein the regioselectivity of this cellulose ester is such, that is, and at aryl-acyl substituted degree (" C2DS of C2 and C3 _aryl" and " C3DS _aryl") aryl-acyl substituted degree (" C6DS of deducting at C6 of sum _aryl") be greater than 0.20.

Another embodiment of the present invention relates to the cellulose ester that a kind of regioselectivity replaces, and it comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent, hydroxyl the substitution value (" DS of the cellulose ester that wherein this regioselectivity replaces _oH") be that about 0.25-is about 0.45, alkyl-acyl substituted degree (" DS of the cellulose ester that wherein this regioselectivity replaces _alkyl") be that about 1.85-is about 2.35, aryl-acyl substituted degree (" DS of the cellulose ester that wherein this regioselectivity replaces _aryl") be that about 0.35-is about 0.65, the regioselectivity of the cellulose ester that wherein this regioselectivity replaces is such, that is, and at aryl-acyl substituted degree (" C2DS of C2 and C3 _aryl" and " C3DS _aryl") aryl-acyl substituted degree (" C6DS of deducting at C6 of sum _aryl") be greater than 0.20.

Another embodiment of the present invention relates to Yi Zhong – A blooming, the cellulose ester that its inclusion region selectivity replaces, and the cellulose ester that wherein this regioselectivity replaces comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent.

Another embodiment of the present invention relates to the cellulose ester that a kind of regioselectivity replaces, and it comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent, hydroxyl the substitution value (" DS of the cellulose ester that wherein this regioselectivity replaces _oH") be that about 0.10-is about 0.30, alkyl-acyl substituted degree (" DS-of the cellulose ester that wherein this regioselectivity replaces _alkyl") be that about 0.10-is about 2.15, aryl-acyl substituted degree (" DS of the cellulose ester that wherein this regioselectivity replaces _aryl") be that about 0.75-is about 2.80, the regioselectivity of the cellulose ester that wherein this regioselectivity replaces is such, that is, and at aryl-acyl substituted degree sum (" C2DS of C2 and C3 _aryl" and " C3DS _aryl") aryl-acyl substituted degree (" C6DS of deducting at C6 _aryl") be at least 0.25.

The present invention's another embodiment still relates to a kind of+C blooming; the cellulose ester that its inclusion region selectivity replaces; the cellulose ester that wherein this regioselectivity replaces comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent, aryl-acyl substituted degree (" DS of the cellulose ester that wherein this regioselectivity replaces _aryl") be about 0.75-about 2.80.

Accompanying drawing explanation

Embodiment of the present invention are here described with reference to accompanying drawing below, wherein:

Fig. 1 (a) schematically illustrates by having polaroid backlight of the pair of orthogonal of two conventional cellulose triacetates (" TAC ") film, the R of each cellulose membrane _e0nm and R _thshi – 40nm;

Fig. 1 (b) has shown the light transmission of the calculating of structure shown in Fig. 1 (a) or the isogram of light leak;

Fig. 2 (a) schematically illustrates backlight by the polaroid of pair of orthogonal, is furnished with Nz and is 0.5 and R between this polaroid _efor the wave plate of 270nm, the zero-lag TAC film that wherein each polaroid comprises contiguous this wave plate;

Fig. 2 (b) has shown the light transmission of the calculating of structure shown in Fig. 2 (a) or the isogram of light leak;

Fig. 3 (a) schematically illustrates backlight by bottom polaroid and top polaroid, and wherein this is quadrature to polaroid, and has the one+A sheet (R being arranged between it _e=137.5nm) and one+C sheet (R _th=100nm), wherein each polaroid comprise respectively with this+A sheet and+zero-lag TAC film that C sheet is adjacent;

Fig. 3 (b) has shown the light transmission of the calculating of structure shown in Fig. 3 (a) or the isogram of light leak;

Fig. 4 is in the cellulosic esterification process being dissolved in dimethyl tricresyl phosphate butyl methyl ammonium (" [TBMA] DMP "), the figure of light absorption ratio to duration of contact; With

Fig. 5 has shown the carbon 13 NMR spectrums of phenylformic acid cellulose propionate (cellulose benzoate propionate).

Embodiment

The present invention can more easily understand with reference to the detailed description below the present invention and the embodiment wherein providing.These should be appreciated that and the invention is not restricted to described concrete grammar, formula and condition, because can change.It is also understood that terminology used here is only used to illustrate the object of the concrete aspect of the present invention, not intend to limit.

In specification sheets and claim subsequently, will mention many terms, it should be defined as the implication having below.

Value may be expressed as " approximately " or " being similar to ", and certain gives fixed number.Similarly, scope may be expressed as from occurrence of " approximately " and/or to " approximately " or another occurrence at this.When expressing such scope, another one aspect has comprised from this occurrence and/or to this another occurrence.Similarly, when use prefix on duty " approximately " is expressed as approximation, be appreciated that this occurrence has formed on the other hand.

In whole the application, mentioning patent or open source literature part, the disclosure of these reference is with their whole the application that are incorporated to by reference, to they not with the inconsistent degree of the present invention, object is to describe more fully the state of the art in field under the present invention.

As mentioned above, the film of being prepared by cellulose ester can be in liquid-crystal display (" LCD ").Conventionally LCD is used the polaroid stacked body of the polaroid that comprises one group of quadrature.For the polaroid of typical one group of quadrature used in LCD, along diagonal lines, can exist obvious light leak (this has caused the contrast gradient of difference), particularly along with visual angle increases and increases.Different bloomings can be for proofreading and correct or " compensation " this light leak.These films can have some double refraction fully defining (or postpone), and it changes the type according to liquid crystal cell used, because liquid crystal cell itself is also by the optical delay that does not make us expectation of giving to a certain degree, it must be proofreaied and correct.Some of these compensate films, than other the manufacture that is easier to, therefore often can be traded off between performance and cost.In addition, although great majority compensation and protective membrane are made by solvent cast, exist the power of manufacturing more film by melt extrusion, object is the needs of eliminating for the disagreeableness solvent of processing environment.The material (its can the two is manufactured by solvent and melt curtain coating) with more controlled optical delay makes to produce these films and has had greater flexibility.

Blooming normally quantizes with degree of birefringence, and it is relevant with refractive index n again.This specific refractory power conventionally can be typically in the scope of 1.4-1.8 for polymkeric substance, and can be in the scope of about 1.46-1.50 for cellulose ester.Specific refractory power is higher, slower through the light wave propagation of this given material.

For the isotropic material of non-orientation, specific refractory power will be identical, no matter the polarization state of the light wave that enters how.During that become orientation when this material or anisotropy, specific refractory power will change according to material direction.In the present invention, exist three kinds of important specific refractory poweres, be called n _x, n _yand n _z, it corresponds respectively to longitudinally (" MD "), horizontal (" TD ") and thickness direction.When material becomes more anisotropy (for example, by stretching), the difference between any two kinds of specific refractory poweres will increase.This species diversity is known as " double refraction ".Because exist the combination of many material directions selective, therefore exist corresponding different birefringence value.Modal two, that is, and planar birefringence rate (or " in face " degree of birefringence) Δ _ewith thickness degree of birefringence (or " face is outer " degree of birefringence) Δ _thbe defined as:

(1a) Δ _e= n _x – n _y

(1b) Δ _th= n _z –(n _x+n _y)/2。

Degree of birefringence Δ _ebe measuring of being orientated in the opposite face between MD and TD direction, and be nondimensional.Contrary Δ _thprovided with respect to mean level of the sea orientation the measuring of the orientation on thickness direction.

Another term that relates to blooming often using is optical delay R.R is the discussed degree of birefringence of film and the simple product of thickness d.Therefore,

(2a) R _e = Δ _ed =(n _x – n _y)d

(2b) R _th = Δ _thd= [n _z –(n _x+n _y)/2]d。

Delay is directly measuring of relative phase shift between the optics ripple of two quadratures, and typically with nanometer (nm) unit, reports.Be noted that R _thto be defined in some authors be different, particularly relate to symbol (+/-), this depends on how to calculate R _th.

Also known materials can change their double refraction/delay behavior.For example most of materials will show along the higher specific refractory power of draw direction with perpendicular to the lower specific refractory power of draw direction when stretching.This is that specific refractory power is typically higher and is lower perpendicular to this chain along the axle of polymer chain because on molecular level.These materials so-called " positive birefringence " and represented the polymkeric substance of most standard, comprise commercially available cellulose ester at present.Be noted that as described after us, positive birefringence material can be for the manufacture of just or negative birefringence film or wave plate.

For fear of obscuring, the double refraction behavior of polymer molecule itself will be known as " intrinsic double refraction ", and be a kind of character of polymkeric substance.Viewpoint from material optics, intrinsic double refraction is that material is stretched completely and whole chains ideally aligns (for most polymers in one direction, this is a theoretical limit, because their complete matchings never) time measures generation is birefringent.In the present invention, also provide measuring of the susceptibility of given polymkeric substance for the chain orientation of specified rate.For example having high intrinsic birefringent sample will show than the larger double refraction of low intrinsic double refraction sample, even relative stress level is roughly the same in film in film forming process.

Polymkeric substance can have positive and negative or zero intrinsic double refraction.Negative intrinsic birefringent polymer shows (with respect to parallel direction) higher specific refractory power on perpendicular to draw direction.Some styrenic and acrylic acid or the like can have negative intrinsic double refraction behavior, and this is owing to their sizable side group.Depend on composition, some cellulose ester with aromatic ring structure also can show negative intrinsic double refraction.By comparison, zero intrinsic double refraction is a kind of Special Circumstances, and does not show double refraction and therefore have zero intrinsic birefringent material while having represented stretching.Such material can be desirable for some optical application because they can be molded in the course of processing, stretch or otherwise pressurization, and do not show any optical delay or distortion.

Actual compensate film for LCD can present various forms, comprises biaxial film, wherein exists whole three kinds of refractive index differences and two optical axises, and has the only uniaxial film of an optical axis, and wherein two in three kinds of specific refractory poweres are identical.The compensate film that also has other types, wherein optical axis distortion or inclination (for example dish-shaped film) on film thickness, but they are normally not too important.The type of the compensate film that conventionally can manufacture is limited to the birefringent characteristic (that is, positive and negative or zero intrinsic double refraction) of polymkeric substance.Several examples are described below.

The in the situation that of uniaxial film, the film with specific refractory power is below known as "+A " blooming

(3a) n _x>n _y=n _z"+A " blooming.

In such film, the x direction (longitudinally) of this film has high refractive index, and y and thickness direction are that about identical magnitude is (and lower than n _x).Such film, also referred to as positive uniaxial crystal structure, has along the optical axis of x direction.Such film can be used for example film drawing machine, by the just intrinsic birefringent material of uniaxial extension, manufactures.

Contrary ， “ – A " uniaxial film is defined as

(3b) nx<ny=nz“ – A " blooming

Wherein x axle specific refractory power is lower than other directions (it is roughly the same).A kind of method of Zao – A blooming processed is the negative intrinsic birefringent polymer that stretches, or, apply from the teeth outwards negative (intrinsic) birefringence liquid crystal polymkeric substance, for example, so that molecule is arranged (passing through the etched oriented layer below using) in preferred direction.

Aspect delay, " ± A " blooming is at R _eand R _thbetween there is lower relation of plane, as shown in (3c):

(3c) R _th=– R _e/ 2 " ± A " blooming.

Another kind of single shaft blooming is C blooming, and it can be also "+C " Huo “ – C ".The difference of C and A blooming is that, in C blooming, exclusive specific refractory power (or optical axis) is on thickness direction rather than in the face of film.Therefore,

(4a) n _z>n _y=n _x"+C " blooming

(4b) nz<ny=nx“ – C " blooming.

C blooming can utilize the stress forming in the solvent cast process of film to produce.In membrane plane, conventionally produce tensile stress, the constraint that this applies owing to casting belt, these tensile stresss are also etc. in essence-biaxial stretch-formed.These tend to chain to arrange in the face of film, for the intrinsic birefringent material of positive and negative respectively Chan Sheng – C or+C film.Because indicating meter many cellulose ester membranes used are solvent casts, and many be positive birefringence substantially, the therefore cellulose ester of solvent cast Chan Sheng – C blooming mostly just obviously.These films also can produce+A of uniaxial extension blooming (delay of supposing initial curtain coating state is low-down).

Except single shaft blooming, can also use Biaxially oriented film.Biaxial film quantizes in many ways, comprises and being simply set forth in main direction 3 kinds of refractive index ns of (with together with the direction of these main axles) _x, n _yand n _z.Common n _x≠ n _y≠ n _z.

A kind of specific Biaxially oriented film has unique optical property and compensates the polaroid of pair of orthogonal or the light leak of face internal conversion (" IPS ") mode LCD.The Parameter N z of this blooming is about 0.4-about 0.9 or equals about 0.5, and wherein Nz is defined as

(5) Nz =(n _x-n _z)/(n _x-n _y)

This parameter has provided with respect to the outer double refraction of birefringent effective surface in face.When compensate film as the polaroid of pair of orthogonal, Nz can be chosen as about 0.5.When Nz is about 0.5, corresponding face external delays R _thequal about 0.0nm.

For the compensation effect of display optical film, by computer Simulation there is and do not have following light transmission or the light leak of polaroid of the pair of orthogonal of compensate film.

Fig. 1 (a) schematically illustrates by having polaroid backlight of the pair of orthogonal of two conventional cellulose triacetates (" TAC ") film, the R of two cellulose membranes _e0nm and R _thshi – 40nm; Fig. 1 (b) shown according to the light transmission of the calculating of the structural texture of Fig. 1 (a) or the isogram of light leak, and its polarizing angle is that 0o-80o and position angle are 0o-360o.The result of this calculating shows the light leak that has about 2.2% along the polaroid axis of homology at 45o.

Fig. 2 (a) schematically illustrates backlight by the polaroid of pair of orthogonal, and this has a Nz=0.5 and R to polaroid _ethe wave plate of=270nm, and two zero-lag TAC film (R _e=0nm and R _th=0nm).Fig. 2 (b) shown according to the light transmission of the calculating of the structural texture of Fig. 2 (a) or the isogram of light leak, and its polarizing angle is that 0o-80o and position angle are 0o-360o.The result of calculating shows to be reduced at the maximum light leak of 45o along the polaroid axis of homology about 0.03%, and this compares with the situation shown in Fig. 1 is a large progress.Therefore, Nz=0.5 and R _ethe wave plate of=270nm can play a role in reducing light leak.Certainly, it is 0.5 and R that such result is not limited only to Nz _e-it is 270 wave plate.For example, this wave plate is Ke Yi Shi – A blooming also, and R _eshi – 270nm etc.If this wave plate is cellulose base ester, it can replace one of zero-lag film, and is directly attached on PVA layer, and this can reduce manufacturing cost again.As described below, the various embodiments that herein propose relate to Nz to be about 0.4-about 0.9 or to be about 0.5 the blooming that comprises cellulose ester (for example wave plate).

Fig. 3 (a) schematically illustrates backlight by the polaroid of pair of orthogonal, and this has one+A blooming (R to polaroid _e=137.5nm), one+C blooming (R _th=100nm) and two zero-lag TAC films (Re=0nm and R _th=0nm).Fig. 3 (b) shown according to the light transmission of the calculating of the structural texture of Fig. 3 (a) or the isogram of light leak, and its polarizing angle is that 0o-80o and position angle are 0o-360o.The result of calculating shows to be reduced at the maximum light leak of 45o along the polaroid axis of homology about 0.04%, and this compares with the situation shown in Fig. 1 is also a large progress.So the positive A postponing shown in having and C blooming have been brought into play effect in reducing light leak.It is to be noted this wave plate also can Shi Yu – C blooming (has for example R _thshi – 100nm) in conjunction with – A blooming, (there is Li as the R of – 137.5nm _e).Gai – A blooming can replace bottom zero-lag film and directly be attached on PVA layer, and this can reduce manufacturing cost again.The various embodiments that herein propose relate to and contain cellulose ester – A blooming.

Simulation embodiment has above confirmed that for example, the light leak of the polaroid of pair of orthogonal can obviously reduce by adding suitable blooming (wave plate).These bloomings also can be for switching the light leak of (" IPS ") mode LCD in complementary area, although because do not wish to be limited to theory, it is believed that the light leak of IPS-LCD mainly comes from the polaroid of this quadrature.

According to various embodiments of the present invention, the cellulose ester that provides regioselectivity to replace, it has a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent.Such cellulose ester can be used to form blooming, its again can be separately or with liquid-crystal display (" LCD ") in be used as wave plate (that is, compensate film) other combination of optical films use.

Be applicable to manufacture the cellulose ester that the regioselectivity of blooming replaces and can comprise a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent.While using herein, term " acyl substituent " will represent to have the substituting group of structure below:

Acyl group such in cellulose ester is bonded on cellulosic pyranose ring via ester bond (that is, passing through Sauerstoffatom) conventionally.

While using herein, term " aryl-acyl group " substituting group will represent that wherein " R " is the acyl substituent of aryl.While using herein, term " aryl " will represent by from aromatic hydrocarbons (that is, and single-or polycyclic aromatic hydrocarbons) in ring carbon on remove the formed monoradical of hydrogen atom, and can comprise heteroatoms.The example that is applicable to the aryl of different embodiments includes but not limited to phenyl, benzyl, tolyl, xylyl and naphthyl.Such aryl can be that replace or unsubstituted.In different embodiments, this aryl-acyl substituent of at least a portion can be benzoic ether.In other embodiments, all or substantially all aryl-acyl substituents can be benzoic ether.

While using herein, term " alkyl-acyl group " will represent that wherein " R " is the acyl substituent of alkyl.While using herein, term " alkyl " by remove the formed monoradical of hydrogen atom from non-aromatics, and can comprise heteroatoms by expression.The alkyl being applicable to herein can be straight chain, branching or ring-type, and can be saturated or undersaturated.The alkyl being applicable to herein comprises any C ₁-C ₂₀, C ₁-C ₁₂, C ₁-C ₅or C ₁-C ₃alkyl.In different embodiments, this alkyl can be C ₁-C ₅straight chained alkyl.In further embodiment, this alkyl can be C ₁-C ₃straight chained alkyl.The object lesson of suitable alkyl includes but not limited to methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, dodecyl, cyclopentyl and cyclohexyl.In one or more embodiments, this alkyl-acyl substituent of at least a portion can be acetic ester, propionic ester and/or butyric ester.In another embodiment, all or substantially all these alkyl-acyl substituents can be acetic ester, propionic ester and/or butyric ester.In further embodiment, this alkyl-acyl substituent can be selected from acetic ester, propionic ester and composition thereof.

The cellulose ester that can use regioselectivity to replace in different embodiments, wherein this aryl-acyl substituent is preferably placed on the C2 and C3 of pyranose ring.Regioselectivity can measure with the relative substitution value at C2 place (" RDS ") by be determined at C6, the C3 of cellulose ester with carbon 13 NMR (Macromolecules, 1991,24,3050-3059).In the situation that the acyl substituent of a type or when there being a small amount of the second acyl substituent (DS < 0.2), this RDS can the most directly determine by the integration of ring carbon.When there is a small amount of 2 kinds or multiple acyl substituent, except measuring ring RDS, sometimes essential with the complete substituted cellulose ester of other substituting group, with the integration by carbonyl carbon, measure independently each substituent RDS.In conventional cellulose ester, regioselectivity does not observe conventionally, and the RDS of C6/C3, C6/C2 or C3/C2 ratio is conventionally close to 1 or lower.Substantially, conventional cellulose ester is random copolymers.On the contrary, when adding one or more acylating agents in the Mierocrystalline cellulose being dissolved in suitable solvent time, this cellulosic C6 position is than C2 and faster ground, C3 position acidylate.Thereby C6/C3 and C6/C2 are greater than 1 than obviously, the feature of the cellulose ester that its regioselectivity that is 6,3-or 6,2-strengthen replaces.

The cellulose ester that regioselectivity replaces and their preparation method's example is described in US2010/0029927, US2010/0267942 and US patent application No.12/539812 (case 80646/US03); Its content is incorporated to by reference at this.In general, these applications relate to and as got off, prepare cellulose ester: cellulose dissolution, in ionic liquid, is then contacted it with acylating agent.Therefore for various embodiments of the present invention, can adopt two kinds of universal methods to prepare the cellulose ester that regioselectivity replaces.In one approach; can adopt segmentation to add to prepare the cellulose ester that regioselectivity replaces: first cellulose solution to be contacted with one or more alkyl acylating agents, be enough to provide the substitution value (" DS ") with expectation to contact with duration of contact with the Contact Temperature of the cellulose ester of the polymerization degree (" DP ") with aryl acylating agent this cellulose solution subsequently.In this segmentation is added, it is upper that the acyl group that contains alkyl can preferentially be arranged on C6, and this acyl group that contains aryl can preferentially be arranged on C2 and/or C3.Or the cellulose ester that this regioselectivity replaces can be as the preparation of getting off: cellulose solution is contacted with one or more alkyl acylating agents, this alkyl ester of separation subsequently, the acyl group that wherein contains alkyl is preferentially arranged on C6.Then this alkyl ester can be dissolved in any suitable organic solvent; and contact with aryl acylating agent, it can be preferentially has the substitution value (" DS ") of expectation and the Contact Temperature of the cellulose ester of the polymerization degree (" DP ") and the acyl group that under duration of contact, this is contained to aryl and is arranged on C2 and/or C3 being enough to provide.The cellulose ester of preparation comprises structure below conventionally thus:

R wherein ₂, R ₃and R ₆hydrogen (but R ₂, R ₃and R ₆when different, be hydrogen), alkyl-acyl group and/or aryl-acyl group (as above-mentioned those), it is bonded on Mierocrystalline cellulose via ester bond.

The polymerization degree of the cellulose ester of preparing by these methods (" DP ") can be at least 10.In other embodiments, the DP of cellulose ester can be at least 50, at least 100 or at least 250.In other embodiments, the DP of cellulose ester can be about 5-about 100 or about 10-about 50.

The acylating agent being applicable to herein can include but not limited to alkyl or aryl carboxylic acid acid anhydride, carboxylic acid halide and/or carboxylicesters, abovementioned alkyl or aryl in its acyl substituent that contains the cellulose ester that is applicable to regioselectivity replacement described herein.The example of suitable carboxylic acid anhydride includes but not limited to diacetyl oxide, propionic anhydride, butyryl oxide and benzoyl oxide.Carboxylic acid halide's example includes but not limited to ethanoyl, propionyl, butyryl radicals and benzoyl muriate.The example of carboxylicesters includes but not limited to ethanoyl, propionyl, butyryl radicals and benzoyl methyl ester.In one or more embodiments, this acylating agent can be one or more carboxylic acid anhydride that are selected from diacetyl oxide, propionic anhydride, butyryl oxide and benzoyl oxide.

In cellulosic esterification process in being dissolved in ionic liquid, this Contact Temperature can be about 140 ℃ of about 20-, approximately about 120 ℃ or about about 100 ℃ of 80-of 50-.In cellulosic esterification process in being dissolved in ionic liquid, can be about 1 minute-about 48 hours this duration of contact, about 10 minutes-about 24 hours or about 30 minutes-about 5 hours.

The cellulose ester that regioselectivity described herein replaces can have different substituting group substitution values.Hydroxyl the substitution value (" DS of the cellulose ester that in certain embodiments, this regioselectivity replaces _oH") can be at least 0.30, at least 0.40, at least 0.50 or about 0.50-about 0.70.Alkyl-acyl substituted degree (" DS of the cellulose ester that in these embodiments, this regioselectivity replaces _alkyl") can be that about 1.60-is about 2.00, approximately 1.60-about 1.90 or approximately 1.65-about 2.00.In addition, in these embodiments, aryl-acyl substituted degree (" DS of the cellulose ester that this regioselectivity replaces _aryl") can be that about 0.50-is about 0.70, approximately 0.60-about 0.70 or approximately 0.50-about 0.68.In such embodiments, the regioselectivity of the cellulose ester that this regioselectivity replaces can be such, that is, and and at aryl-acyl substituted degree sum (" C2DS of C2 and C3 _aryl" and " C3DS _aryl") aryl-acyl substituted degree (" C6DS of deducting at C6 _aryl") be greater than 0.20, for about 0.22-about 0.50 or be about 0.25-about 0.45.

The DS of the cellulose ester that in certain other embodiments, this regioselectivity replaces _oHcan be about 0.25-about 0.45.The DS of the cellulose ester that in these embodiments, this regioselectivity replaces _alkylcan be that about 1.85-is about 2.35, approximately 1.85-about 2.25 or approximately 1.95-about 2.35.The DS of the cellulose ester that in addition in these embodiments, this regioselectivity replaces _arylcan be that about 0.35-is about 0.65, approximately 0.40-about 0.65 or approximately 0.35-about 0.60.In such embodiments, the regioselectivity of the cellulose ester that this regioselectivity replaces can be such, that is, and and C2DS _aryland C3DS _arylsum deducts C6DS _arylbe greater than 0.20, for about 0.21-about 0.45 or be about 0.23-about 0.40.

In further embodiment, the DS of the cellulose ester that this regioselectivity replaces _oHcan be about 0.10-about 0.30.The DS of the cellulose ester that in these embodiments, this regioselectivity replaces _alkylcan be that about 0.10-is about 2.15, approximately 0.75-about 2.05 or approximately 1.20-about 1.85.The DS of the cellulose ester that in addition in these embodiments, this regioselectivity replaces _arylcan be that about 0.75-is about 2.80, approximately 0.80-about 2.00 or approximately 1.00-about 1.60.In such embodiments, the regioselectivity of the cellulose ester that this regioselectivity replaces can be such, that is, and and C2DS _aryland C3DS _arylsum deducts C6DS _arylat least 0.25, approximately 0.30-about 1.10 or approximately 0.70-about 1.05.Or the regioselectivity of the cellulose ester that this regioselectivity replaces in these embodiments can be such, that is, and C2DS _aryland C3DS _arylsum deducts C6DS _arylabout 0.25-about 0.80 or about 0.50-about 0.70.

As mentioned above, certain embodiments of the present invention relate to single layer optical film.In different embodiments, such single layer optical film can be single shaft or biaxial optical film.In addition, the Nz of such single layer optical film can be that about 0.40-is about 0.90, approximately 0.45-about 0.78 or about 0.50.The face external delays of this single layer optical film (is determined according to formula 2 (b) above; " R _th") be great Yue – 50 is to approximately+50nm, about 0 to approximately+50nm or about 0 to approximately+20nm.In the face of this single layer optical film, postpone in addition (according to formula 2 (a) above, to determine; " R _e") be great Yue – 100 is to great – 300nm Yue, great is – 170 to great – 290nm or great – 200 to great – 270nm Yue Yue Yue Yue.

Such single layer optical film can comprise the cellulose ester that one or more above-mentioned regioselectivities replace.In different embodiments, the cellulose ester that this single layer optical film can inclusion region selectivity replaces, the DS of the cellulose ester that described regioselectivity replaces _oHat least 0.30, at least 0.40, at least 0.50 or about 0.50-about 0.70; DS _alkylthat about 1.60-is about 2.00, approximately 1.60-about 1.90 or approximately 1.65-about 2.00; And DS _arylthat about 0.50-is about 0.70, approximately 0.60-about 0.70 or approximately 0.50-about 0.68.In addition, this single layer optical film can comprise the cellulose ester with such regioselectivity, that is, and and C2DS _aryland C3DS _arylsum deducts C6DS _arylbeing greater than 0.20, is approximately 0.22-about 0.50 or approximately 0.25-about 0.45.In different embodiments, the cellulose ester that such regioselectivity replaces can account at least 50 % by weight of all or all single layer optical films substantially, at least 75 % by weight, at least 95 % by weight, at least 99 % by weight.

As mentioned above, certain embodiments of the present invention She is Ji – A blooming.As the above ， – A blooming, be that those specific refractory poweres meet equation: nx<ny, n whereinyapproximate greatly nzfilm.In different embodiments, the Nz of Zhe Yang – A blooming can be about 0.95-about 1.50 or about 0.97-about 1.10.The R of Gai – A blooming of ， in additionthcan be that about+150nm is arrived in about+50, approximately+100nm be arrived to about+125nm or about+75 in approximately+70.In addition the R of Gai – A bloomingecan be great Yue – 100 is to great – 300nm Yue, great is – 120 to great – 220nm or great – 150 to great – 200nm Yue Yue Yue Yue.

Zhe Yang – A blooming can comprise the cellulose ester that one or more above-mentioned regioselectivities replace.The cellulose ester that Gai – A blooming of ， can inclusion region selectivity replaces in different embodiments, the DS of the cellulose ester that described regioselectivity replaces _oHabout 0.25-about 0.45; DS _alkylthat about 1.85-is about 2.35, approximately 1.85-about 2.25 or approximately 1.95-about 2.35; And DS _arylthat about 0.35-is about 0.65, approximately 0.40-about 0.65 or approximately 0.35-about 0.60.Gai – A blooming can comprise the cellulose ester with such regioselectivity in addition, that is, and and C2DS _aryland C3DS _arylsum deducts C6DS _arylbeing greater than 0.20, is approximately 0.21-about 0.45 or approximately 0.23-about 0.40.In different embodiments, the cellulose ester that such regioselectivity replaces can account at least 50 % by weight of all or Suo You – A blooming substantially, at least 75 % by weight, at least 95 % by weight, at least 99 % by weight.

As mentioned above, relate to+C of certain embodiments of the present invention blooming.As mentioned above ,+C blooming is that those specific refractory poweres meet equation: n _z>n _y, n wherein _yequal n _xfilm.In different embodiments, the R of such+C blooming _thcan be that about+800nm is arrived in about+50, approximately+150nm be arrived to about+400nm or about+50 in approximately+50.The R of be somebody's turn to do in addition ,+C blooming _ecan be great Yue – 15 to approximately+15nm, great Yue – 10 to approximately+10nm, great Yue – 5 to approximately+5nm or about 0nm.

Like this+C blooming can comprise the cellulose ester that one or more above-mentioned regioselectivities replace.In different embodiments, should+cellulose ester that C blooming can inclusion region selectivity replaces, the DS of the cellulose ester that described regioselectivity replaces _oHabout 0.10-about 0.30; DS _alkylthat about 0.10-is about 2.15, approximately 0.75-about 2.05 or approximately 1.20-about 1.85; And DS _arylthat about 0.75-is about 2.80, approximately 0.80-about 2.00 or approximately 1.00-about 1.60.Be somebody's turn to do in addition+C blooming can comprise cellulose ester, and its regioselectivity is such, that is, and and C2DS _aryland C3DS _arylsum deducts C6DS _arylat least 0.25, approximately 0.30-about 1.10 or approximately 0.70-about 1.05.Or the regioselectivity of the cellulose ester that in+C blooming, regioselectivity used replaces can be such, that is, and C2DS _aryland C3DS _arylsum deducts C6DS _arylabout 0.25-about 0.80 or about 0.50-about 0.70.In different embodiments, the cellulose ester that such regioselectivity replaces can account at least 50 % by weight of all or all+C blooming substantially, at least 75 % by weight, at least 95 % by weight, at least 99 % by weight.

The mean thickness of any above-mentioned blooming can be the about 120 μ m of about 40-, the approximately about 70 μ m of 40-or the approximately about 20 μ m of 5-.While using herein, " mean thickness " is average by least three equally spaced observed values of expression optical film thickness.

In different embodiments, the cellulose ester that the regioselectivity used with the above-mentioned blooming of preparation such as additive such as softening agent, stablizer, UV absorption agent, anti-caking agent, antiseize paste, lubricant, dyestuff, pigment, delay properties-correcting agent can be replaced mixes.The example of these additives can for example find in U.S. Patent Application Publication No.US2009/0050842, US2009/0054638 and US2009/0096962, and its content is incorporated to by reference at this.

Any above-mentioned blooming can be manufactured by solvent cast, melt extrusion, laminated or coating method.These programs normally prior art are known.Solvent cast, melt extrusion, example laminated or coating method can for example find in U.S. Patent Application Publication No.US2009/0050842, US2009/0054638 and US2009/0096962, and its content is incorporated to by reference at this.Solvent cast, melt extrusion, laminated or coating method form the other example of film can be for example U.S. Patent No. 4592885 and 7172713 and U.S. Patent Application Publication No.US2005/0133953 and US2010/0055356 in find, its content is incorporated to by reference at this.

In order to help to obtain with the cellulose ester that regioselectivity described herein replaces the R of expectation _eand R _thvalue, described film can stretch.By adjusting stretching condition, as annealing time and the temperature after draft temperature, stretching type (single shaft or twin shaft), stretch ratio, warm up time and temperature and stretching, can realize the R of expectation _eand R _th.Accurate stretching condition can depend on that the concrete composition of cellulose ester of this regioselectivity replacement is, the second-order transition temperature of the amount of softening agent and type and concrete composition.Therefore concrete stretching condition can change widely.In different embodiments, draft temperature can be about 200 ℃ of about 160-.In addition, the stretch ratio based on longitudinal (" MD ") upper 1.0 can be about 1.3-about 2.0 on horizontal (" TD ").Can be the about 300s of about 10-warm up time, and preheating temperature can be identical with draft temperature.The after annealing time can be the about 300s of about 0-, and after annealing temperature can be than about 40 ℃ of the low about 10-of draft temperature.Film thickness can depend on film thickness and the stretching condition before stretching.After stretching, film thickness can be the about 500 μ m of about 1 μ m-, the about 200 μ m of about 5 μ m-or the about 120 μ m of about 10 μ m-.

Except optical property, the prepared film of cellulose ester that described regioselectivity replaces from here also has other valuable features.The cellulose ester of LCD many routines used in showing has relatively high water absorbability, and it has affected dimensional stability and has caused the optical value of the film of variation.The prepared film of cellulose ester that this described regioselectivity replaces from here has low water absorbability, and the optical value of this film changes very little under high humidity and high temperature.Therefore in different embodiments, the cellulose ester that this regioselectivity replaces can comprise the moisture that is less than 2 % by weight, is less than the moisture of 1 % by weight or is less than the moisture of 0.5 % by weight.In other different embodiments, when at 60 ℃, 100% relative humidity storage is in the time of 240 hours, the R of cellulose ester membrane _evariation can be less than 4%, be less than 1% or be less than 0.5%.

The cellulose ester that regioselectivity described herein replaces is heat-staple surprisingly, and this makes them is very useful in the melt extrusion of film.Therefore an aspect of of the present present invention relates to the cellulose ester that regioselectivity replaces, and it has at 330 ℃, 340 ℃ or 350 ℃ the loss that is less than 10 % by weight of measuring by thermogravimetric analysis.

As mentioned above, blooming described herein can be in LCD.Particularly, above-mentioned blooming can be as all or all compensate films in the polaroid stacked body of LCD.As mentioned above, polaroid stacked body generally includes the polaroid of two quadratures of the both sides that are arranged in liquid crystal layer.Compensate film can be between liquid crystal layer and a polaroid.In one or more embodiments, above-mentioned single layer optical film can be alone as the compensate film (that is, wave plate) in LCD.In such embodiments, this single layer optical film can be between a polaroid of liquid crystal layer and LCD.In other embodiments, above stating – A blooming can be in the compensate film in LCD (that is, wave plate).In such embodiments, the adjacent layout of blooming that this-– A blooming can be other with at least one, wherein so other blooming Ke Yi Shi – C blooming.In other embodiments, above-mentioned+C blooming can be in the compensate film in LCD (that is, wave plate).In such embodiments, should+the adjacent layout of blooming that C blooming can be other with at least one, wherein so other blooming can be+A blooming.In any foregoing embodiments, the prepared LCD that comprises blooming described herein can carry out work with face internal conversion (" IPS ") pattern.

Blooming described herein also can be in rotatory polarization sheet.Particularly, can prepare single quarter-wave plate, it comprises one or more above-mentioned bloomings of the present invention, and it can be for converting linearly polarized photon to circularly polarized light.This aspect to for circularly polarized three-dimensional (" 3-D ") glass and/or 3-D mediavisualizer for example TV (" 3-D TV ") may be valuable especially.Therefore in one or more embodiments, can prepare the single quarter-wave plate that comprises above-mentioned single layer optical film.In other different embodiments, can prepare the single quarter-wave plate that comprises Shu – A blooming.Such quarter-wave plate can be applied to the on glass of 3-D TV, for example, on polarization stacked body.In addition, such quarter-wave plate can be applied to the on glass of 3-D glass.The in the situation that of 3-D glass, can use this blooming, make an optical axis in lens perpendicular to or be basically perpendicular to the optical axis of another lens.Result in 3-D glass is that some observed polarization is obstructed in lens, but will, through other lenses, produce viewed 3-D optical effect.In different embodiments, the polaroid that the quarter-wave plate that comprises one or more above-mentioned bloomings can be other with at least one (it can be linear polarizer plate) is collaborative to be used.

The present invention can further illustrate by the following example of its embodiment, but should be appreciated that unless otherwise expressly indicated, and these embodiment add the only object for illustrating, not intends to limit the scope of the invention.

Embodiment

Materials and methods

universal program:

NMR characterizes: proton N MR data are to obtain on the JEOL type Eclipse-600 NMR spectrometer with 600 MHz operations.Sample hose size is 5mm, and sample concentration is about 20mg/mL DMSO-d ₆.Each spectrum is to record with 64 scannings and the pulse delay of 15 seconds at 80 ℃.1 to 2 trifluoroacetic acid-d is added in each sample, to move residual water from interested spectrum region.Chemical shift is with DMSO-d ₆central peak as internal reference (2.49ppm), use from the displacement of tetramethylsilane with PPM (" ppm ") report.

Quantitative carbon 13 NMR data are to obtain on the JEOL type GX-400 NMR spectrometer with 100MHz operation.Sample hose size is 10mm, and sample concentration is about 100mg/mL DMSO-d ₆.Acetyl Acetone acid chromium (III) is added to each sample as relaxant with 5mg/100mg cellulose ester.Each spectrum is typically at 80 ℃, with rushing of 10000 scanning and 1 second arteries and veins, postpones to record.Chemical shift is with DMSO-d ₆central peak as internal reference (39.5ppm), use from the displacement of tetramethylsilane with ppm report.

The proton of cellulose ethanoate of the present invention and cellulose propionate and carbon NMR spectrum point out based on macromolecules, 1987,20,2750 Hes macromolecules, 1991,24, the work described in 3050.Benzoic ether carbonyl carbon resonance point out based on chirality, 2000,12, the work described in 670.

The acetic ester (" DS of acyl group phenylformic acid Mierocrystalline cellulose (cellulose acyl benzoate) _ac"), propionic ester (" DS _pr") and benzoic ether (" DS _bz") substitution value be by ¹h NMR measures.As an example, the DS of CBzP _prcan be as the calculating of getting off: first 0.3-1.2ppm is composed to the integration in district divided by 3 (the substituent methyl resonance of propionic ester), it is the result divided by 7 (proton resonances of anhydroglucose ring) divided by the integration in the spectrum region of 2.7-5.8ppm then.Similarly, the DS of CBzP _bzcan be as the calculating of getting off: first 7.0-8.2ppm is composed to the integration in district divided by 5 (the substituent phenyl ring proton resonances of benzoic ether), it is the result divided by 7 (proton resonances of anhydroglucose ring) divided by the integration in the spectrum region of 2.7-5.8ppm then.Then can deduct DS with 3 _pr+ DS _bzsum is calculated DS _oH.

The cellulosic relative substitution value of acyl group phenylformic acid (" RDS ") is measured by carbon 13 NMR.The resonance center of unsubstituted C6 carbon is at 60.0ppm.After the esterification of C6 place, resonance is to low (downfield) skew, and center is in 62.5ppm.The RDS of C6 can by by the integration of the resonance of 62.5ppm divided by 60.0 and the integration sum of the resonance of 62.5ppm calculate.The esterification of alcohol has caused the high field offset of carbon atom γ to carbonyl.Therefore,, for cellulose ester, in the esterification of C2, be reflected in unsubstituted C1 carbon resonance (center is at 102.3ppm) to the high field offset of 99.4ppm.Based on this, at the RDS of C2, can calculate by the integration of these carbon resonances.Similarly, in the esterification of C3, be reflected in the high field offset of unsubstituted C4 carbon resonance (center is at 79.6ppm).The resonance of C4 carbon resonance and the resonance part of C2, C3 and C5 carbon that replace are overlapping.But, can be as lower calculating at the RDS of C3: by the integration of unsubstituted C4 carbon resonance divided by C1 and C6 carbon resonance sum divided by 2 result.With 1, deduct the RDS that income value is given in C3.

C6DS _bzand C2DS _bz+ C3DS _bzthat the integration resonating by benzoic ether carbonyl carbon is determined.The integration in 164.6-165.8ppm spectrum region has provided corresponding to C6 _bzpart, the integration in 163.4-164.6ppm spectrum region has provided corresponding to C2 _bz+ C3 _bzpart.C6DS _bzand C2DS _bz+ C3DS _bzthen can use obtained C6 _bzand C2 _bz+ C3 _bzintegral part be multiplied by by ¹the DS that H NMR obtains _bzcalculate.

Solution preparation: cellulose ester solid and 10wt% softening agent are joined to CH ₂cl ₂or 90/10CH ₂cl ₂in/acetone, produce the ultimate density of 12wt%, based on cellulose ester+softening agent.By the sealing of this mixture, be placed on roller, and mix and within 24 hours, produce homogeneous solution.

Use scraper curtain coating to sheet glass the solution of preparing above, obtain the film with expectation thickness.Curtain coating is carried out in stink cupboard, and relative humidity is controlled at 45% ~ 50%.After curtain coating, this film is dried to 45 minutes under shrouding disc, to make the vaporator rate of solvent minimum before removing shrouding disc.This film is dried to 15 minutes, then this film is peeled from glass, and at 100 ℃, anneal 10 minutes in air-supply stove.After 100 ℃ of annealing, this film is annealed other 10 minutes at higher temperature (120 ℃).

Film stretches and completes by Br ü ckner Karo IV lab membrane drawing machine.Stretching condition can affect final optical delay and the dispersiveness of film as stretch ratio, draft temperature, preheating and after annealing.Stretching condition offers each sample subsequently below.

Film optical delay and dispersed measurement are to carry out with the J.A.Woollam M-2000V light splitting ellipsometer of spectral range 370-1000nm.Use is from J.A.Woollam Co., and the RetMeas of Inc. (delay measurements) program obtains (R in optics face _e) and the outer (R of face _th) postpone.

Embodiment 1. N _zblooming: add and prepare phenylformic acid cellulose propionate (DS by segmentation _pr=1.91, DS _bz=0.62) and measure optical property.(EX1020-114)

To the dimethyl tricresyl phosphate butyl methyl ammonium (" TBMADMP ") that adds 81.85g in the 3 neck round-bottomed flasks of 300mL.This TBMADMP is heated to 100 ℃, wherein it is kept to 3h at 0.68-1.20mmHg.Add N-Methyl pyrrolidone (NMP, 35.04g, 30wt%) in this TBMADMP, and by this solution cool to room temperature.To DPv 657 Mierocrystalline celluloses (4min interpolation) that add 8.79g (7wt%) in this solution.By this non-homogeneous mixture at stirring at room 1h 40min.After inserting the IR probe for in-situ monitoring reaction (Mettler-Toledo AutoChem, Inc., Columbia, MD, USA), mixture is heated to 100 ℃.This mixture is stirred to a whole night (15h 10min) at 100 ℃, and it provides transparent homo-fibre cellulose solution.

In this cellulose solution, add 9.88g (1.4 equivalent) propionic anhydride (3min interpolation).Starting to add propionic anhydride after 12 minutes, IR shows that all propionic anhydrides are consumed (Fig. 4).Take out sample, cellulose propionate is next separated by precipitating with MeOH.After filtration, this sample is cleaned 4 times to subsequent drying white solid (5mmHg, 50 ℃) with MeOH. ¹h NMR analyzes the DS that shows this sample _pr=1.13 and propionic ester be mainly positioned at C6.After taking out sample, by the Bz of 34.3g (2.8 equivalent) ₂o adds (2min interpolation) in remaining solution as solid.Except corresponding to Bz ₂o at 1788cm ^-1outside band, by IR, observe corresponding to Pr at once ₂o at 1818cm ^-1band (Fig. 4).This is considered to owing to Bz ₂o reacts with residual propionic acid from the first step of reaction, has caused forming the acid anhydrides and/or the Pr that mix ₂o.Owing to the light absorption ratio of these two bands along with time slow decreasing, and at 1724cm ^-1(carboxylic acid) be with corresponding enhancing.From starting to add Bz ₂after O 2h 5min, IR shows that all acid anhydrides consume.This phenylformic acid cellulose propionate is next separated by precipitating with MeOH.After filtration, this sample is cleaned 10 times to subsequent drying white solid (5mmHg, 50 ℃) with MeOH. ¹h NMR analyzes the DS that shows this sample _pr=1.91 and DS _bz=0.62. ¹³c NMR analyzes and shows that relative substitution value is: C6=1.00, C3=0.63, C2=0.83.The integration resonating by benzoic ether carbonyl, ¹³c NMR also shows C2DS _bz+ C3DS _bz– C6DS _bz=0.35 (Fig. 5).

Use this phenylformic acid cellulose propionate (DS _pr=1.91, DS _bz=0.62), according to general film curtain coating program, carry out casting films (CH ₂cl ₂).Then according to general film stretching run this film that stretches.The results are summarized in table 1.

Table 1. is by the R of the prepared non-stretching and stretched film of phenylformic acid cellulose propionate _eand R _th(DS _pr=1.91, DS _bz=0.62):

¹use the warm up time of 25s and the speed of 14%/s to stretch all samples.

As shown in this embodiment, (the Pr that first adds therein 1.4 equivalents is added in segmentation ₂o) produced the cellulose propionate of DS=1.13, it is upper that wherein propionic ester is mainly positioned at C6, and have less on C2 and C3.By adding Bz ₂o, has formed the mixture of acid anhydrides, itself and Mierocrystalline cellulose competing reaction.Formed phenylformic acid cellulose propionate has than the Pr based on added ₂the desired higher DS of equivalents of O _pr(DS _pr=1.91), this is owing to having formed mixed acid anhydride.Result is DS _bz=0.62 phenylformic acid cellulose propionate, wherein benzoic ether is mainly positioned on C2 and C3.When film is to use to be dissolved in CH ₂cl ₂in this CBzP curtain coating and when 1x1.6 (MDxTD) stretches, formed film (sample 3) R under the film thickness of 70 μ m _ebe-221nm and R _thbe 41nm, it is desirable for preparation Nz blooming.Under lower stretch ratio (1x1.3 or 1x1.4), R _eabsolute value less, but be suitable for Nz blooming.

Embodiment 2. N _zblooming: add and prepare phenylformic acid cellulose propionate (DS by segmentation _pr=2.03, DS _bz=0.51) and measure optical property.(EX1020-127)

According to the universal program shown in embodiment 1, prepared phenylformic acid cellulose propionate (DS _pr=2.03, DS _bz=0.51).By ¹³c NMR has measured the relative substitution value (" RDS ") of this phenylformic acid cellulose propionate.Total RDS of this sample is C6=1.00; C3=0.64 and C2=0.84.For benzoic ether, replace the benzoic ether substitution value sum (C2DS that the regioselectivity of this sample makes at C2 and C3 _bz+ C3DS _bz) the benzoic ether substitution value (C6DS that deducts at C6 _bz) be 0.33.

With this phenylformic acid cellulose propionate, according to general film curtain coating and stretching run, carry out curtain coating (CH ₂cl ₂) and stretched film.The results are summarized in table 2.

Table 2. is by the R of the prepared non-stretching and stretched film of phenylformic acid cellulose propionate _eand R _th(DS _pr=2.03, DS _bz=0.51):

¹use the warm up time of 25s and the speed of 14%/s to stretch all samples.

This embodiment shows the increase along with stretch ratio, R _eand R _ththe absolute value of the two increases.For example, under identical thickness (76 μ m), stretch ratio changes to 1x1.50 from 1x1.40, R _efrom-112.4 increase to-124.7nm and R _thfrom 5.0, increase to 41.1nm (sample 4 and 5).Thickness when this embodiment has also shown film stretching and the importance of temperature.When stretching for 172 ℃, the R of membrane sample 6 _ebe-162.0nm and R _th43.9nm.When draft temperature is reduced to 170 ℃ and film thickness and increases to 94 μ m (sample 7), R _eincrease to-216.7nm, but R _th(41.5nm) with respect to sample 6 is basic, do not become.As shown in this embodiment, when this film is while stretching according to optimum condition of the present invention, DS _bz=0.51 phenylformic acid cellulose propionate (wherein propionic ester is mainly positioned on C2 and C3) is suitable for Nz blooming.

Embodiment 3. N _zblooming: add and prepare phenylformic acid rhodia (DS by segmentation _ac=1.81, DS _bz=0.62) and measure optical property.(EX1020-122)

According to the universal program of embodiment 1, prepare phenylformic acid rhodia (DS _ac=1.81, DS _bz=0.62).In this case, the Ac that first adds 1 equivalent ₂o, adds the Bz of 3.4 equivalents subsequently ₂o.The relative substitution value of this phenylformic acid rhodia (" RDS ") be by ¹³c NMR measures.Total RDS of this sample is C6=1.00; C3=0.57 and C2=0.78.For benzoic ether, replace the benzoic ether substitution value sum (C2DS that the regioselectivity of this sample makes at C2 and C3 _bz+ C3DS _bz) the benzoic ether substitution value (C6DS that deducts at C6 _bz) be 0.44.

With this phenylformic acid rhodia, according to general film curtain coating and stretching run, carry out curtain coating (90/10CH ₂cl ₂/ acetone) and stretched film.The results are summarized in table 3.

The R of the non-stretching and stretched film that phenylformic acid rhodia that table 3. is replaced by regioselectivity is prepared _eand R _th(DS _ac=1.81, DS _bz=0.62):

This embodiment show when this film be while stretching according to optimum condition of the present invention, DS _bz=0.62 phenylformic acid rhodia (wherein benzoic ether is mainly positioned on C2 and C3) is also suitable for Nz blooming.With respect to CBzP, need higher draft temperature, this is owing to the difference of the second-order transition temperature between this cellulose ester of two types.This embodiment also shows R _eand R _ththe absolute value of the two increases (comparative sample 9 and 10) along with the increase of stretch ratio.Be similar to CBzP, the importance of thickness and temperature when this embodiment has also shown film stretching.When draft temperature drops to 190 ℃ from 195 ℃, R _efrom-132.0 increase to-164nm (comparative sample 10 and 11), and R _thkeep relatively constant, although the film of sample 11 thicker (80 μ m).

(comparative example, US2009/0082557) by esterified cellulose, hydrolysis subsequently, then arranges that benzoic ether prepares phenylformic acid rhodia propionic ester (DS to embodiment 4. _bz=0.62), and measure optical property.(EX368-13)

According to the method (US2009/0096962) described in the people such as Shelton, by first cellulose ester being changed into three esters, the cellulose acetate propionate that a kind of non-regioselectivity replaces is prepared in hydrolysis subsequently.This method typically produces has high C6 DS _oHcellulose ester (DS for example _pr=1.77, DS _ac=0.16, C6 RDS=0.56, C3 RDS=0.71, C2 RDS=0.66).

To the anhydrous pyridine that adds 1L in the 3 neck flasks of 2L.When stirring, the cellulose acetate propionate that the non-regioselectivity of 65.05g is replaced adds in this pyridine.This non-homogeneous mixture is heated to 50 ℃, at this CAP that names a person for a particular job, slowly dissolves.After dissolving, slowly add (20min interpolation) Benzoyl chloride (33.3g).By this solution at N ₂under at 50 ° of C, stir 20h, be then cooled to 24 ℃.Then this contact mixture is slowly joined in the ethanol of 8L strong stirring.By formed solid by filtration separation with the other ethanol of 8L, clean.After dry, obtained 77g pale solid.Proton N MR shows the DS of CbzAP _bz=0.62.Because initial CAP has high C6 DS _oH, this benzoic ether is mainly positioned on C6.On the contrary, this benzoic ether is mainly arranged on the C2 and C3 of Mierocrystalline cellulose acyl group benzoic ether of the present invention.

According to general film curtain coating and stretching run, carry out curtain coating (90/10CH ₂cl ₂/ THF) and stretched film.The results are summarized in table 4.

The R of stretched film prepared by the phenylformic acid rhodia propionic ester that table 4. is replaced by non-regioselectivity _eand R _th:

¹use the warm up time of 25s and the speed of 14%/s to stretch all samples.

This embodiment has shown DS _bzthe phenylformic acid cellulose propionate (this benzoic ether is mainly positioned on C6 therein) that=0.62 non-regioselectivity replaces is unsuitable for Nz blooming, no matter the stretching condition using how.In all cases, R _etoo low, and R _thnormally excessive.

(comparative example, US2009/0082557) by esterified cellulose, hydrolysis subsequently, then arranges that benzoic ether prepares phenylformic acid rhodia (DS to embodiment 5. _bz=0.86), and measure optical property.(EX368-27)

According to the universal method described in embodiment 4, first cellulose ester is changed into three esters, the cellulose ethanoate that a kind of non-regioselectivity replaces is prepared in hydrolysis subsequently.The DS of formed cellulose ethanoate _ac=1.78.

According to the program described in embodiment 4, prepared CBzA.Proton N MR has shown the DS of this CbzAP _bz=0.86.Because initial CA has high C6 DS _oH, this benzoic ether is mainly positioned on C6.

According to general film curtain coating and stretching run, carry out curtain coating (90/10CH ₂cl ₂/ THF) and stretched film.The results are summarized in table 5.

The R of stretched film prepared by the phenylformic acid rhodia that table 5. is replaced by non-regioselectivity _eand R _th:

¹use the warm up time of 25s and the speed of 14%/s to stretch all samples.

This embodiment shows (DS _bz=0.86) the phenylformic acid cellulose propionate (benzoic ether is mainly positioned on C6 therein) that non-regioselectivity replaces is unsuitable for Nz blooming, no matter the stretching condition using how.In all cases, R _eall too low, and R _thnormally excessive.

Embodiment 6. – A bloomings: add and prepare phenylformic acid cellulose propionate by segmentation, and measure optical property.(EX1020-97，106，111)

According to the universal program shown in embodiment 1, prepare phenylformic acid cellulose propionate.Adjust Pr ₂o and Bz ₂the equivalents of O obtains DS and the optical value (table 6) of expectation.The benzoic ether substitution value sum (C2DS that the regioselectivity of sample 30-32 (being prepared by identical phenylformic acid cellulose propionate) makes at C2 and C3 _bz+ C3DS _bz) the benzoic ether substitution value (C6DS that deducts at C6 _bz) be 0.38.The benzoic ether substitution value sum (C2DS that the regioselectivity of sample 33 and 34 (being prepared by identical phenylformic acid cellulose propionate) makes at C2 and C3 _bz+ C3DS _bz) the benzoic ether substitution value (C6DS that deducts at C6 _bz) be 0.23.The benzoic ether substitution value sum (C2DS that the regioselectivity of sample 35 and 36 (being prepared by identical phenylformic acid cellulose propionate) makes at C2 and C3 _bz+ C3DS _bz) the benzoic ether substitution value (C6DS that deducts at C6 _bz) be 0.38.

According to general film curtain coating and stretching run, carry out curtain coating (CH ₂cl ₂) and stretched film.The results are summarized in table 6.

The R of non-stretching and stretching – A film prepared by the phenylformic acid cellulose propionate that table 6. is replaced by regioselectivity _eand R _th:

This embodiment show when this film be while stretching according to optimum condition of the present invention, the DS in range of choice _bzand DS _oHinterior phenylformic acid cellulose propionate Shi Yu – A blooming.The Nz scope of sample is 1.44-0.97 like this, and its Dui Yu – A blooming is desirable.

Embodiment 7. C+ bloomings: add to prepare Mierocrystalline cellulose acyl group benzoic ether by segmentation, and measure optical property.(EX1020-68-3，EX1020-85-2，EX1020-81-3，EX1020-90-3，EX1020-72-2，EX1020-56-3，EX1020-84-2，EX1020-69-3，EX1020-80-3，EX1020-83-3，EX1020-86-2)

According to the universal program shown in embodiment 1, prepare phenylformic acid cellulose propionate.Adjust alkyl acid anhydrides and Bz ₂the equivalents of O obtains DS and the optical value (table 7) of expectation.In addition, for alkyl acid anhydrides and Bz ₂o, adds order and has also changed.For example, for first adding the prepared sample (sample 37,39,40,42 and 44-47) of alkyl acid anhydrides (diacetyl oxide, propionic anhydride or caproic anhydride), the benzoic ether substitution value sum (C2DS that the regioselectivity of this Mierocrystalline cellulose acyl group benzoic ether makes at C2 and C3 _bz+ C3DS _bz) the benzoic ether substitution value (C6DS that deducts at C6 _bz) scope is 0.30-1.06.For first adding the prepared sample of benzoyl oxide (sample 38,41 and 43), the benzoic ether substitution value sum (C2DS that the regioselectivity of this Mierocrystalline cellulose acyl group benzoic ether makes at C2 and C3 _bz+ C3DS _bz) the benzoic ether substitution value (C6DS that deducts at C6 _bz) scope is 0.25-0.76.

According to general film curtain coating program, carry out casting films (CH ₂cl ₂), but do not stretch.Anhydride equivalent, interpolation order and formed DS value are summarised in table 7.When at Bz ₂while adding aliphatic anhydride before O, by other aliphatic anhydride at Bz ₂after O, add.Adopt this scheme to guarantee DS _oHlow-down, to eliminate DS _oHimpact for optical property.In most of the cases, the 3rd add optional because the 3rd add before DS _oHquite low.Thickness and optical results are summarised in table 8.By R _eand R _thvalue be normalized into 60 μ m and 20 μ m, with the film thickness identical directly relatively and show that these Mierocrystalline cellulose acyl group benzoic ethers are used as the effectiveness of the suprabasil coating of film.

The anhydride equivalent of table 7. Mierocrystalline cellulose acyl group benzoic ether, interpolation order and gained DS value:

Table 8. is by thickness, the R of the C+ film of different acyl group phenylformic acid Mierocrystalline cellulose curtain coatings _eand R _th.R _eand R _thbe normalized into 60 μ m and 20 μ m:

Sample	d(μm)	R _e	R _th	R _e60(nm)	R _th60(nm)	R _e20(nm)	R _th20(nm)
								37	64	3.3	190.5	3.5	173.7	1.2	57.9
38	68	6.7	137.2	4.2	118.6	1.4	39.5
								39	60	5.7	143.7	7.3	143.5	2.4	47.8
40	70	0.9	125.1	1.6	108.9	0.5	36.3
								41	94	12.4	580.1	9.2	363.2	3.1	121.0
42	66	6.6	549.5	12.1	495.5	4.1	165.6
								43	62	2.4	201.1	2.8	196.4	0.9	65.5
44	84	48	358.5	29.1	267.3	9.7	89.1
								45	76	4.3	228.7	3.1	183.7	1.0	61.2
46	70	2.0	138.5	1.4	117.3	0.5	39.1
								47	92	7.6	279.5	3.6	192.3	1.2	64.1

This embodiment has shown the of the present invention many key characters that relate to C+ blooming.First, comparative sample 42,44,45 and 47, they are by first adding Pr ₂o, at all Pr ₂o adds Bz after consuming subsequently ₂then O adds Pr ₂prepared by O, observe R _thalong with DS _bzincrease and increase.That is the level that, improves benzoic ether has improved R _thabsolute size.The second, the interpolation order remarkably influenced of acid anhydrides R _thsize.For example sample 41 is as the preparation of getting off: the Bz that first adds 4.5 equivalents ₂o, at all Bz ₂o adds 2 equivalent Pr after consuming subsequently ₂o.The DS of sample 41 _bz=1.98 and R _ththe 60th, 363.2nm.Sample 42 is as the preparation of getting off: the Pr that first adds 1 equivalent ₂o, at all Pr ₂o adds 5 equivalent Bz after consuming subsequently ₂o, then adds the Pr of 2 equivalents ₂o.The DS of sample 42 _bz=1.61 and R _ththe 60th, 495.5nm.That is, even if sample 42 has the DS lower than sample 41 _bz, the R of sample 42 _th60 remain obviously larger.When comparative sample 37-38 and sample 43-44, can observe similar behavior.In each case, arrange acyl group on C6, preferentially on C2 and C3, arrange benzoic ether subsequently, this has caused larger R _thvalue.The 3rd, by comparative sample 44 (CBzP, DS _bz=1.13, R _th60=267.3nm) with sample 37 (CBzA, DS _bz=1.09, R _th60=173.7nm), can see when acyl group is propionic ester and acetic ester R _thlarger.The 4th, many R in these samples _th20 are greater than 50nm, and this is suitable in the preparation of C+ blooming as the suprabasil shallow layer of film them.That is, preferentially on C2 and C3, arrange that the benzoic ether of proper level has caused large R _thvalue is also even like this in film.Finally, sample 40 and 46 R _th20 show DS _bztoo low and these Mierocrystalline cellulose acyl group benzoic ethers are unsuitable for C+ blooming.

Definition

Be to be understood that it is the complete list of term of definition that following content is not intended to.Other definition in above stated specification, may be provided, for example, when being accompanied by the use of term of definition in context.

While using herein, term " ", " a kind of " and " being somebody's turn to do " represent one or many.

While using herein, term "and/or" is when the list for two or more project, and expression can be used separately any one of Listed Items or can use the arbitrary combination of two or more Listed Items.If for example composition is described to contain component A, B and/or C, said composition can comprise independent A; Independent B; Independent C; The combination of A and B; The combination of A and C, the combination of the combination of B and C or A, B and C.

While using herein, term " is comprising ", " comprising " and " including " be open transitional term, for the theme quoted, be transitioned into one or more elements of quoting after this term from this term, wherein after this transitional term listed element need not to be form described theme only have an element.

While using herein, term " has ", " having " with identical open implication is provided " comprising " of providing above, " comprising " and " including ".

While using herein, term " is comprising ", " comprising " and " including " with identical open implication is provided " comprising " of providing above, " comprising " and " including ".

Digital scope

This specification sheets quantizes some parameter relevant with the present invention with digital scope.Be to be understood that when digital scope is provided, such scope is interpreted as only using the claim of the lower value of this scope to limit and only having used the claim restriction of the higher limit of this scope that word support is provided.For example disclosed digital scope 10-100 provides word support for having the claim of the restriction of " being greater than 10 " (there is no the upper limit) with the claim with the restriction of " being less than 100 " (there is no lower limit).

This specification sheets has used concrete numerical value to quantize some parameter relevant with the present invention, and wherein these concrete numerical value are not clear and definite parts of digital scope.Be to be understood that each the concrete numerical value providing is interpreted as providing word support to the scope with narrow wide, centre here.The wide region relevant with each concrete numerical value be this numerical value add and deduct this numerical value 60%, be rounded up to two significant figures.The intermediate range relevant with each concrete numerical value be this numerical value add and deduct this numerical value 30%, be rounded up to two significant figures.The close limit relevant with each concrete numerical value be this numerical value add and deduct this numerical value 15%, be rounded up to two significant figures.If for example specification sheets has been described concrete temperature 62 ℉, such description provides word support to the narrow digital scope of the wide digital scope of 25 ℉-99 ℉ (62 ℉ +/-37 ℉), the sandwich digit scope of 43 ℉-81 ℉ (62 ℉ +/-19 ℉) and 53 ℉-71 ℉ (62 ℉ +/-9 ℉).These digital scopes with narrow wide, centre should not be only applicable to this occurrence, and should also be applicable to the difference between these occurrences.If therefore specification sheets has been described the first pressure 110psia and the second pressure 48psia (difference 62psi), the scope with narrow wide, centre of the pressure difference between these two fluids will be respectively 25-99psi, 43-81psi and 53-71psi.

Claim is not limited to disclosed embodiment

The preferred form of the invention described above, only with explaining, should not make for explaining scope of the present invention with restrictive, sense.Those skilled in the art easily make improvements above-mentioned exemplary, and do not depart from purport of the present invention.

The inventor states that they are intended to rely on doctrine of equivalents to determine and assess fair and reasonable scope of the present invention hereby, such as but it is suitable for not having substantive the disengaging any equipment within the literal scope of the present invention that claim not is below set forth.

Claims

1. the cellulose ester that regioselectivity replaces, it comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent, hydroxyl the substitution value (" DS of the cellulose ester that wherein said regioselectivity replaces _oH") be that about 0.10-is about 0.30, alkyl-acyl substituted degree (" DS-of the cellulose ester that wherein said regioselectivity replaces _alkyl") be that about 0.10-is about 2.15, aryl-acyl substituted degree (" DS of the wherein said cellulose ester replacing for regioselectivity _aryl") be that about 0.75-is about 2.80, the regioselectivity of the cellulose ester that wherein this regioselectivity replaces is such, that is, and at aryl-acyl substituted degree sum (" C2DS of C2 and C3 _aryl" and " C3DS _aryl") aryl-acyl substituted degree (" C6DS of deducting at C6 _aryl") be at least 0.25.

2. the cellulose ester that the regioselectivity of claim 1 replaces, the DS-of the cellulose ester that wherein said regioselectivity replaces _alkylfor about 0.75-about 2.05, the DS of the cellulose ester that wherein said regioselectivity replaces _arylfor about 0.80-about 2.00.

3. the cellulose ester that the regioselectivity of claim 1 replaces, the DS-of the cellulose ester that wherein said regioselectivity replaces _alkylfor about 1.20-about 1.85, the DS of the cellulose ester that wherein said regioselectivity replaces _arylfor about 1.00-about 1.60.

4. the cellulose ester that the regioselectivity of claim 1 replaces, the aryl of wherein said aryl-acyl substituent comprises phenyl replacement or unsubstituted, and the alkyl of wherein said alkyl-acyl substituent comprises C ₁-C ₅straight chained alkyl.

5. the cellulose ester that the regioselectivity of claim 1 replaces, wherein said aryl-acyl substituent comprises benzoic ether, and wherein said alkyl-acyl substituent comprises acetic ester and/or propionic ester.

6. the cellulose ester that the regioselectivity of claim 1 replaces, the regioselectivity of the cellulose ester that wherein said regioselectivity replaces is such, that is, and C2DS _arylwith C3DS _arylsum deducts C6DS _arylfor about 0.30-about 1.10.

7. one kind+C blooming; the cellulose ester that its inclusion region selectivity replaces; the cellulose ester that wherein said regioselectivity replaces comprises a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituent, aryl-acyl substituted degree (" DS of the cellulose ester that wherein said regioselectivity replaces _aryl") be about 0.75-about 2.80.

Claim 7+C blooming, hydroxyl the substitution value (" DS of the cellulose ester that wherein said regioselectivity replaces _oH") be that about 0.10-is about 0.30, alkyl-acyl substituted degree (" DS-of the cellulose ester that wherein said regioselectivity replaces _alkyl") be about 0.10-about 2.15.

Claim 7+C blooming, the DS-of the cellulose ester that wherein said regioselectivity replaces _alkylfor about 0.75-about 2.05, the DS of the cellulose ester that wherein said regioselectivity replaces _arylfor about 0.80-about 2.00.

Claim 7+C blooming, the DS-of the cellulose ester that wherein said regioselectivity replaces _alkylfor about 1.20-about 1.85, the DS of the cellulose ester that wherein said regioselectivity replaces _arylfor about 1.00-about 1.60.

11. claims 7+C blooming, the aryl of wherein said aryl-acyl substituent comprises phenyl replacement or unsubstituted, and the alkyl of wherein said alkyl-acyl substituent comprises C ₁-C ₅straight chained alkyl.

12. claims 7+C blooming, wherein said aryl-acyl substituent comprises benzoic ether, and wherein said alkyl-acyl substituent comprises acetic ester and/or propionic ester.

13. claims 7+C blooming, the regioselectivity of the cellulose ester that wherein said regioselectivity replaces is such, that is, and at aryl-acyl substituted degree sum (" C2DS of C2 and C3 _aryl" and " C3DS _aryl") aryl-acyl substituted degree (" C6DS of deducting at C6 _aryl") be at least 0.25.

14. claims 7+C blooming, the R of wherein said+C blooming _thfor approximately+50 are to approximately+800nm, the R of described+C blooming _efor great, Yue – 15 is to approximately+15nm, and the thickness of wherein said+C blooming is about 40 to about 120 μ m.

15. claims 7+C blooming, the R of wherein said+C blooming _thfor approximately+50 are to approximately+400nm, the R of described+C blooming _efor great, Yue – 10 is to approximately+10nm, and the thickness of wherein said+C blooming is the about 70 μ m of about 40-.

16. claims 7+C blooming, the R of wherein said+C blooming _thfor approximately+50 are to approximately+150nm, the R of described+C blooming _efor great, Yue – 5 is to approximately+5nm, and the thickness of wherein said+C blooming is the about 20 μ m of about 5-.

17. 1 kinds of liquid-crystal displays that comprise compensate film (" LCD "), wherein said compensate film comprise claim 7 described+C blooming.

The LCD of 18. claims 17, wherein said LCD carrys out work with face internal conversion (" IPS ") pattern.

The LCD of 19. claims 17, wherein said compensate film comprises and+at least one other blooming that C blooming is adjacent.

The LCD of 20. claims 19, wherein said other blooming is+A blooming.